Frontiers of Chemical Science and Engineering
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2021
·Vol. 16
·期 3
·384-396
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IF 4.204
Liu Xiangyu,Pan Yanling,Zhang Peng,Wang Yilin,Xu Guohao,Su Zhaojie,Zhu Xuedong,Yang Fan
Alkylation of benzene to value-added, high octane number and low toxic toluene and xylenes provides a way to lower benzene content in gasoline pool, and is hence a method to promote fuel quality. On the other hand, CO 2 accumulation in the atmosphere causes global warming and requires effective route for its valorization. Utilization of CO 2 as a carbon source for benzene alkylation could achieve both goals. Herein, alkylation of benzene with CO 2 and H 2 was realized by a series of low-cost bifunctional catalysts containing zinc/titanium oxides (Zn/Ti oxides) and HZSM-5 molecular sieves in a fixed-bed reactor. By regulating and controlling oxygen vacancies of Zn/Ti oxides and the acidities of HZSM-5, benzene conversion and CO 2 conversion reached 28.7% and 29.9% respectively, along with a total selectivity of toluene and xylene higher than 90%. In this process, more than 25% CO 2 was effectively utilized and incorporated into the target products. Moreover, the mechanism of the reaction was analyzed and the course was simultaneously traced. CO 2 was transformed into methanol firstly, and then methanol reacted with benzene generating toluene and xylene. The innovation provides a new method for upgrading of fuels and upcycling the emissions of CO 2 , which is of great environmental and economic benefits.
研究领域:
化学工程
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环境科学
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催化科学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2021
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IF 3.764
Zhongwen Dong,Xinyi Wang,Weifeng Chu,Chuanyu Yang,Yanan Wang,Lin Mei,Dongpu Zhao,Wenjie Xin,Shenglin Liu,Hongxia Wang,Yongchen Shang,Longya Xu
A fast synthetic methodology of β-zeolite with the assistance of γ-butyrolactone (GBL) has been developed in this paper, and the synthetic parameters are systematically investigated to obtain β-zeolite efficiently. Compared to the conventional synthetic system with a crystallization time of 120 h, GBL promotes the crystallization of β-zeolite in a much shorter time of 24 h. An accelerated nucleation mechanism of β-zeolite assisted by GBL is unraveled by X-ray diffraction, scanning electron microscopy, thermogravimetry–differential thermal analysis, Fourier transform infrared spectroscopy, and NMR techniques. The results demonstrate that GBL can adjust the pH value of the initial gels and enhance the combination of TEA+ with aluminosilicate species; in the meantime, the Hoffmann degradation of TEAOH is suppressed. In addition, the β-catalyst obtained with the assistance of GBL exhibits both a higher selectivity of tert-butylbenzene and excellent catalytic stability in the alkylation of benzene with isobutylene compared with the commercial β-catalyst with a similar SiO2/Al2O3 molar ratio.
研究领域:
化学工程
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催化材料
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS LETTERS
·
2023
·
IF 2.8
Zhang Yakun,Xu Lin,Wang Wen,Wu Qing,Zhang Yi
The efficient conversion of ethane has attracted more and more attention because of the shale gas revolution. The coupling of ethane dehydrogenation (EDH) and benzene alkylation over the 1.5Pt/HZSM-5 realize high activity close to the thermodynamic equilibrium of EDH at 500 ℃ and 0.9 bar ethane partial pressure. Meanwhile, the coupled reaction shows long-term stability during 22 h with a slightly decreased ethane conversion of 0.03% per hour and as high as 42% selectivity of ethylbenzene. Based on various characterization, including XRD, HR-TEM, NH 3 -TPD, Py-IR, TGA, it is confirmed that the coupling reaction could convert ethylene, formed by EDH over Pt sites, to ethylbenzene via benzene alkylation over Brönsted acidic sites (BAS) subsequently, and suppressing the sintering of Pt species and coke deposition induced by aromatization and deep dehydrogenation, resulting in high activity and long-time steady state. Graphical Abstract
研究领域:
化学工程
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Kairui Zhang,Qiong Tang,Lei Liu,Jinxiang Dong
The alkylation reaction of benzene with n- butene can not only significantly improve the utilization rate of n- butene, but also solve the shortage problem of phenol and methyl ethyl ketone, and alleviate the surplus problem of acetone. This study demonstrates a strategic approach to engineering hierarchical ZSM-5 zeolites with controlled aluminum distributions for enhanced benzene-butene alkylation catalysis. Through aluminum precursor selection (aluminum isopropoxide, sulfate, and sodium aluminate) coupled with resin-templated synthesis, the framework Al speciation and mesopore architecture in ZSM-5 could be regulated. Advanced characterization revealed that aluminum source chemistry governs Brønsted/Lewis acid ratios, Al spatial positioning (sinusoidal/straight channels), and mesopore volume. The synthetic hierarchical ZSM-5 zeolites exhibited significant difference in catalytic performance toward benzene-butene alkylation, the Al atoms in HZ5-AIP zeolite with the largest pore size mainly in straight and sinusoidal channels, achieving 99 % conversion of n -butene (210 °C, 3 MPa, benzene/butene molar ratio = 5:1, WHSV Bu = 6 h −1 ).
研究领域:
催化化学
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材料科学
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石油化工
✓ 已验证
DOI
高影响因子
Catalysis Science & Technology
·
2016
·Vol. 6
·期 8
·2647-2652
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IF 5.287
Hualei Hu,Jinghui Lyu,Jiayao Rui,Jie Cen,Qunfeng Zhang,Qingtao Wang,Wenwen Han,Xiaonian Li
Ethylbenzene is the major side product in benzene alkylation with methanol and it is difficult to be suppressed over hierarchical porous ZSM-5. Moreover, the separation of ethylbenzene from xylene still remains a great challenge. Our research indicated that ethylbenzene formation could be highly suppressed by changing the Si/Al ratio of the catalyst. Hierarchical porous ZSM-5 catalysts with different Si/Al ratios were prepared via reducing the amount of Al in the solvent evaporation assisted dry gel conversion method. In this method, tetra-n-propylammonium hydroxide was used as the direct agent to create micropores, and hexadecyltrimethoxysilane was added to create additional porosities by forming organic assemblies which occupied a certain space between zeolitic walls. The catalyst with a Si/Al ratio of 1800 could achieve high benzene conversion (59.5%) and high xylene selectivity (39.0%) as well as excellent suppression of ethylbenzene formation (<0.1%).
研究领域:
催化化学
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材料科学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2022
·
IF 5.723
Guoqiang Hou,Tingjun Fu,Xin Li,Qian Ma,Zhong Li
HZSM-5 catalysts with abundant silanol nests were fabricated by removing framework Al, which effectively promoted the selective alkylation of toluene with methanol by inhibiting the deep alkylation of aromatics to heavy aromatics and the conversion of methanol to light hydrocarbons. Correspondingly, the alkylation efficiency reached 65.3% at a toluene conversion of 31.3% over dealuminated HZSM-5, higher than the 55.2% efficiency and 28.0% conversion of parent zeolites, respectively. In situ DRIFTS and single-factor experimental clarified that toluene adsorption was enhanced and methanol to hydrocarbons was inhibited with the presence of silanol nests. Additionally, by increasing the crystal size of HZSM-5 with silanol nests from 2 to 5 µm, para-xylene selectivity was increased from 36.1% to 65.5% because of the enhanced diffusion barrier . The finding of the positive effect of the silanol nests on toluene alkylation can provide a solid fundamental basis for the rational design of catalysts.
研究领域:
催化化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY
·
2017
·Vol. 90
·期 1
·149-155
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IF 1.095
Dong Peng,Li Zeyu,Ji Dong,Wang Xiaorui,Yun Hongfei,Du Zhisong,Bian Jie,Li Guixian
Modified Y type catalyst (M-Y) shows great potential for the preparation of toluene attribute to catalyst topology and synergistic effect of Lewis acid and Brönsted acid in the alkylation reaction. However, it still remains a big challenge to build a reaction mechanism. Thereby, based on the study of HZSM-5, H-beta and M-Y catalysts structure and physical properties, a plausible reaction mechanism was proposed. The samples were characterized by X-ray diffraction, N 2 adsorption/desorption, Fourier transform infrared absorption spectra and Pyridine adsorption infrared. The activity of catalysts was tested in benzene alkylation with methanol and was found to be in the following increasing order: Na-Y (no effect) < H-Y << HZSM-5 < H-beta < M-Y.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
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2021
·
IF 5.455
Jun Liang,Yingying Wang,Xiangcheng Li,Ming Xu,Shaochun Shen,Chuang Liu,Wenhua Fu,Weichuan Tao,Zhiqing Yuan,Zhendong Wang,Weimin Yang
A novel quaternary ammonium hydroxide , p-Xylylene-bis(N-methylpiperidinium hydroxide) (XBMPOH), was prepared and used as an organic structure-directing agent (OSDA) for the syntheses of BEC zeolites . Both Si,Ge- BEC and Al incorporated BEC (Al- BEC ) zeolites were successfully synthesized. In comparison with commonly used OSDA (tetraethylammonium hydroxide (TEAOH)), XBMPOH was more suitable for the crystallization of BEC structure, especially in the Al containing system. Al- BEC zeolites were directly synthesized at lower germanium and OSDA content, in a wider (Si + Ge)/Al ratio range (20 to ∞ vs. 50 to ∞) and shorter time (6 h vs. 12 h). For the first time, Al- BEC zeolites were used as a solid acid to catalyze the alkylation of benzene with 1-dodecene, and showed significant catalytic performance. After an acidic treatment procedure, the catalytic performance was further improved due to the removal of non-framework Al with accompanied exposure of framework Al.
研究领域:
化学工程
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材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2023
·Vol. 17
·期 4
·404-414
·
IF 4.5
Cheng Junjun,Zhao Yitao,Xu Guohao,Zhang Peng,Zhu Xuedong,Yang Fan
Alkylation of benzene with carbon dioxide and hydrogen to produce toluene and xylene could increase the added-value of surplus benzene as well as relieve environmental problems like green-house effect. In this work, the alkylation benzene with carbon dioxide and hydrogen reaction was proceeded by using the mixture of zinc-zirconium oxide and HZSM-5 as bifunctional catalyst. The equivalent of Zn/Zr = 1 displays the best catalytic performance at 425 °C and 3.0 MPa, and benzene conversion reaches 42.9% with a selectivity of 90% towards toluene and xylene. Moreover, the carbon dioxide conversion achieves 23.3% and the carbon monoxide selectivity is lower than 35%, indicating that more than 50% carbon dioxide has been effectively incorporated into the target product, which is the best result as far as we know. Combined with characterizations, it indicated that the Zn and Zr formed a solid solution under specific conditions (Zn/Zr = 1). The as-formed solid solution not only possesses a high surface area but also provides a large amount of oxygen vacancies. Additionally, the bifunctional catalyst has excellent stabilities that could keep operating without deactivation for at least 80 h. This work provides promising industrial applications for the upgrading of aromatics.
研究领域:
催化化学
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环境科学
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材料科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2021
·
IF 13.273
Xiangyou Kong,Pengfei Nie,Ling Shi,Maocong Hu,Pingping Zhang,Xia Li,Zhiyi Wang,Xuguang Liu
Fast synthesis of zeolite with hydrothermal method is a challengeable topic. In this work, we reduced the crystallization time to ~1/3 of conventional method by adding a small amount of graphene oxide (GO) into ZSM-11 synthesis gel. The embedment of GO into ZSM-11 crystal was confirmed by XPS, TG, and Raman spectra, while it modified morphology, porosities, component, and surface acidity of ZSM-11 as characterized by SEM, TEM, XRF, N 2 -physisorbtion, NH 3 -TPD, and Py-IR. The non-classical nucleation, which governed the required crystallization time, was further proposed and evidenced by both experimental observations and molecular dynamic modeling. It clearly illustrated the positive role of GO on promoting the formation of meta-stable phase during non-classic nucleation, resulting into much shorter crystallization time. GO embedded ZSM-11 demonstrated high activity (reaction rate and TOF), improved selectivity, and superior stability for benzene alkylation with ethanol, which can be attributed to the regulated surface acidity and diffusion properties. This work opens up a new perspective to synthesize ZSM-11 zeolite with superior catalytic performance in a highly efficient and environmental manner.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED ORGANOMETALLIC CHEMISTRY
·
2021
·Vol. 35
·期 4
·e6147
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IF 4.105
Sujuan Ge,Yuming Zhou,Xiaoli Sheng,Chunfeng Mao,Lina Zhao,Jianxing Xu,Lei Qiu
Piperidinium-based ionic liquids (ILs) were synthesized under mild conditions by coordinating N -alkyl- N -methylpiperidinium bromide ([Pip 1,x ]Br) with anhydrous AlCl 3 . The weak basicity of N -methylpiperidine had little impact on downstream problems from proton impurities and catalyst poisoning. The results of Fourier transform infrared (FT-IR), electrospray ionization mass spectrometry (ESI-MS), and nuclear magnetic resonance ( 27 Al NMR) confirmed that the active components in [Pip 1,x ]Br-2AlCl 3 ( χ = 0.67) were [Al 3 Cl 9 Br] − and [Al 2 Cl 6 Br] − . Besides, the reaction performance of [Pip 1,8 ]Br-2AlCl 3 under different conditions was carried out by single-factor experiment and further confirmed by orthogonal experimental method. Among these reaction conditions, the optimal combination was the reaction temperature of 40°C, ILs/O molar ratio of 0.2:1, px/O molar ratio of 12:1, and the reaction time of 30 min. Furthermore, [Pip 1,8 ]Br-2AlCl 3 had excellent stability and can be recycled 14 times. It was the high-efficiency catalytic activity and prominent recyclability that made continuous industrial production possible.
研究领域:
化学工程
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催化科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Ben Liang,Meng-Nan Liu,Ning An,Fang Ren,Qun-Xing Luo,Huiyong Chen,Jun Hu,Xiaoxun Ma,Qing-Qing Hao
The environmentally benign and long-lived zeolite catalyst is highly desired for Friedel-Crafts (FC) alkylation of benzene with long-chain olefins. Herein, MWW zeolites with different layer arrangements and surface structures are employed as model catalysts to investigate the effects of microscale structure on the catalytic behaviors for the alkylation of benzene with 1-dodecene. It is revealed that two kinds of acid sites located on the external surface and within surface 12-membered ring (12MR) pockets of MWW zeolites are effective for this reaction. Unexpectedly, the turnover frequency (TOF) of the effective acid sites over single-layer MWW (SL-MWW) is significantly lower than that of MCM-22. Kinetic study indicates that apparent activation energy ( E a ) is decreased in the order of MCM-36 > MCM-22 > SL-MWW. Combined with DFT calculation, the lowest TOF and E a over SL-MWW can be reasonably attributed to the higher proportion of acid sites in the 12MR pockets and its higher diffusional limitation for products. Moreover, the highest E a of MCM-36 and adsorption energy verified the decreased diffusion limitation of 12MR pockets due to the structure defect resulting from the desilication. Finally, the highly efficient and stable MCM-36 catalyst was achieved in the optimal reaction conditions, which is a potential catalyst for industrial application in the field of FC alkylation reactions.
研究领域:
化学工程
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催化科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
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